The present invention relates to an article resistant to attack from environmental contaminants under high temperature conditions, the article being of the type comprising a metal alloy part, a thermal barrier coating deposited onto the metal alloy part, and a protective top coat of a material different from the material of the thermal barrier coating deposited onto the thermal barrier coating.
Articles of this type are used, for example, as metal alloy parts in gas turbine engines operating under high temperature conditions. The thermal barrier coatings reduce the heat flow into the coated metal part during operation of the engine, and allow the metal part to run cooler than the gas stream, thereby extending part life and resulting in a higher combustion efficiency by permitting higher gas temperatures.
Conventional thermal barrier coatings are comprised of ceramic materials, for example chemically-stabilized zirconia, including yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia, calcia-stabilized zirconia and magnesium zirconia, with YSZ being the thermal barrier coating of choice. These coatings are bonded to the surface of the metal part or to an intermediate metal bond coat.
A conventional thermal barrier coating is porous. It usually contains a degree of porosity ranging from 3-20%. The pores and any small micro-cracks also present in the material are not well-connected. Therefore, environmental contaminants do not have a ready path from the coating surface to the metal-ceramic interface. In use, these small micro-cracks lengthen and subsequently provide an easy, or more direct path for contaminants to reach the metal surface. The propagation and extension of micro-cracks is due to a combination of operating factors including, but not limited to, high temperature, high pressure, coating erosion by particulates, particle impact, chemical reactions and stress caused by differential thermal expansion. Some gases may also react with the thermal barrier coating to form molten salts that may effectively penetrate the micro-cracks and connected pores. Subsequent failure of the coating, which is also referred to as delamination or spalling, is a result of the corrosion of the metal at the metal-ceramic interface or within the ceramic layer adjacent to the metal.
The prior art describes certain techniques which aim to impede or reduce damage to the thermal barrier coatings, thus extending the service life of the protected metal parts.
There is a considerable body of information available regarding the numerous alternate methods of increasing thermal protection of the parent metal and/or extending the life of the ceramic coatings. This includes data in the open literature [Journal of Thermal Spray Technology, Journal of Engineering for Gas Turbines and Power, Engineered Materials Handbook Vol. 4 (Ceramics and Glasses) Section 11 (ASM International, 1991), etc.] and patent protected data. Coatings that consist of a metal bond layer with a single ceramic thermally insulating top coat have generally concentrated on improved oxidation resistant metal bond coats and more erosion, corrosion or thermal shock resistant ceramic coatings. The use of 8% yttria stabilized zirconia instead of 20% yttria stabilized zirconia and the development of ceria stabilized zirconia [Siemers et al., U.S. Pat. No. 4,328,285 (1982)] are typical examples. Bruce et al. U.S. Pat. No. 5,683,761 discloses the use (in certain applications) of pure alpha alumina, as a means of obtaining higher erosion resistance and lower density (than zirconia). Similarly, graded layers have been used, for improved thermal shock resistance. These approaches do not all have a single ceramic coating. Also, these coatings fail before failure of layers below them. They are xe2x80x9csacrificialxe2x80x9d coatings.
Hasz el al. U.S. Pat. Nos. 5,871,820 issued on Feb. 16, 1999 and 5,851,678, issued on Dec. 22, 1998 describe a method for protecting a thermal barrier coating from environmental contaminants and a coating protected by the method. A top coat in the form of an impermeable, non-porous barrier coating is deposited onto the surface of the thermal barrier coating. This non-porous, impermeable barrier coating is intended to prevent the environmental contaminants from coming into contact with the ceramic thermal barrier coating.
U.S. Pat. No. 5,773,141 issued to Hasz et al. on Jun. 30, 1998 describes the provision of a top coat in the form of a single protective layer of a sacrificial or reactive oxide that overlays the outer surface of the thermal barrier coating. The sacrificial layer reacts with liquid contaminants to increase the viscosity or melting temperature of these contaminants. This inhibits chemical attack on the underlying thermal barrier. Since this protective layer reacts with the environment and is progressively depleted with continued use, it is said to be sacrificial, and will protect the thermal barrier coating for a limited period of time.
Bruce et al. U.S. Pat. No. 5,683,761 describes the use of pure alpha alumina as a top coat over zirconia ceramic coatings. The alpha alumina coating is used to increase erosion resistance and fails, by erosion or cracking, before the underlying zirconia coating is affected. That is, it is a sacrifical coating. Similarly, Voss et al. U.S. Pat. No. 6,006,516 describes the use of low porosity mullite over zirconia, to provide a chemically inert surface. This mullite coating must have lower porosity than the underlying zirconia, be smoother than the zirconia and fails before the underlying zirconia. Voss et al. describe the need for increased coating thickness for increased protection.
The present invention is concerned with the provision of thermal barrier coatings with increased resistance to attack by environmental contaminants at high temperature conditions.
In accordance with one aspect of the present invention, an article as described above is characterized in that:
the top coat is non-sacrificial;
the top coat is porous;
the top coat is substantially thinner than the thermal barrier coating;
the top coat is a material selected from the group consisting of ceria stabilized zirconia (CSZ); calcium-stabilized zirconia (CaSZ); zirconia toughened alumina (ZTA); a compound oxide other than mullite and modified mullite ceramics; and mixtures of two or more thereof; and
the top coat is selected from materials more resistant to the environmental contaminants than the base thermal barrier coating.
It has been shown that the use of a top coat with these characteristics provides good protection for the thermal barrier coating. The top coat protects the thermal barrier coating in several ways, depending on the environmental contaminants and conditions present:
1. The protective top coat covers and encases the thermal barrier coating, providing a physical barrier on the surface of the thermal barrier coating and thereby substantially reducing the rate of infiltration of molten environmental contaminants into the thermal barrier coating.
2. The protective top coat provides a chemical barrier minimizing the chemical interaction of the contaminant environment with the thermal barrier coating, thereby significantly slowing down the chemical dissolution of the thermal barrier coating at high operating temperatures.
3. Since the top coat is selected not to react with environmental contaminants, adherence of these contaminants to the surface is resisted and the migration of these contaminants into the thermal barrier coating is accordingly minimised. In addition, most of the deposits that may form on the surface of the thin protective top coat are only loosely adhered to the surface and are quickly removed by the high velocity gas flowing over the surface, or during cool down owing to the consequent differential thermal expansion.
4. In environments where particulate impact or erosion may occur, a higher resistance in the thin protective top layer of the present invention reduces the rate of microcracking of the base ceramic layer, thereby extending the life of the coating.
For gas turbine applications of the invention, the metal alloy part, which may also be referred to as the parent material, may be of any material used in the construction of engine parts. The metal alloy part may, for example, comprise cobalt, iron, chromium, nickel, aluminum, or an alloy of two or more of those metals. When used, a metal bond coat may be comprised, for example, of a metal superalloy, or a metal alloy comprised of cobalt, iron, chromium, nickel, aluminum, or any other appropriate metal alloy material.
Compound oxides that may be used in the protective top coat may comprise two or more compounds from the group consisting of oxides of aluminum, cobalt, chromium, iron, titanium and nickel. The term xe2x80x9ccompound oxidesxe2x80x9d is to be construed as not including mullite, which is, in any case, specifically excluded by the foregoing description.
The protective thermal barrier coating may comprise yttria-stabilized zirconia (YSZ), alumina-titania, calcia stabilized-zirconia, magnesia stabilized-zirconia, ceria-stabilized zirconia (CSZ), scandia stabilized-zirconia, calcium silicate, calcium silicate zirconate blends, calcium-stabilized zirconia (CaSZ), zirconia toughened alumina (ZTA), alumina-zirconia, zirconium silicate, zircon, alumina or blends thereof.
The preferred ceramic of the thermal barrier coating is yttria-stabilized zirconia (YSZ) while the preferred protective top coat deposited thereon will depend on the specific environmental conditions faced.
Articles configured according to the present invention may be subjected to attack from various environmental contaminants. These may include oxygen, sodium, chlorine and saline mixtures, water vapour, vanadium, sulfur and similar contaminants under high temperature conditions. These contaminants may be carried by high velocity combustion gas streams at temperatures from 850xc2x0 C. (1560xc2x0 F.) to 1200xc2x0 C. (2204xc2x0 F.) or higher. The parts may be subjected to continuous, long term exposure or thermally cycled exposure.
Both the base ceramic layer and the top protective layer may be deposited by thermal spraying (plasma or flame) or from a slurry or by sol-gel techniques. When deposited from a slurry or sol-gel, a subsequent heat treatment will be required to dry the coating and provide the necessary cohesive and adhesive strength.
Where the top coat comprises compound oxides, those oxides may include two or more compounds from the group consisting of oxides of aluminum, cobalt, chromium, iron titanium and nickel. A compound oxide top coat is preferably deposited by plasma or flame thermal spray processes, however, slurry and sol-gel techniques may be used as well, with a subsequent heat treatment.
The top coat is a porous but continuous layer, of thickness between 25 and 125 microns (0.001 and 0.005 inches), and porosity between 1 and 20%. Preferably, the top coat will be 25-50 microns (0.001-0.002 inches) thick with 3-10% pore content. Lower pore content than the underlying ceramic coating is not necessary.
The reduction or prevention of contaminants into the thermal barrier coating reduces the occurrence of fracture at or near the thermal barrier coating-metal interface, which may also be referred to as the ceramic-metal interface. The reduction and prevention of the infiltration of contaminants into the ceramic layer of the thermal barrier coating and the subsequent infiltration of contaminants to or near to the ceramic-metal interface reduces the occurrence of delamination, prevents failure of the thermal barrier coating and consequently maintains the integrity of the thermal barrier coating and extends the life of the metal alloy part.
It should be noted that the properties of the protective top coat materials are not all identical. The selection of which protective top coat will be deposited onto the thermal barrier coating should be based on the specific needs and use requirements of the metal alloy part. For example, at temperatures less than 1000xc2x0 C. (1832xc2x0 F.) a protective top coat of calcium silicate zirconate (CaSZ) or compound oxides may provide better protection than a protective top coat of ceria-stabilized zirconia (CSZ) or zirconia toughened alumina (ZTA), whereas the reverse may be true at temperatures exceeding 1000xc2x0 C. (1832xc2x0 F.).
The present protective top coat is useful in preserving the thermal barrier coating from the contaminant environments of operating gas turbines. However, the utility of the top coat is not limited to that operating environment. It is also suitable for hot section gas turbine parts as well as other machine parts, which may encounter high operating temperatures or undergo thermal cycling. For example, the present protective coating may serve as a useful protective coating in a variety of industrial fields, such as steam engines, boilers, standard air engines, marine atmospheres, petrochemical and metal refineries.
The thickness of the protective top coat may vary, but the preferred thickness is essentially determined by the amount of protective coating needed to prevent the infiltration of environmental contaminants into the thermal barrier coat. The protective top coat of the present invention is thin with respect to the ceramic layer of the thermal barrier coating it encases. The thickness of the protective top coat may be approximately one fifth the thickness of the ceramic layer of the thermal barrier coating thereunder. Preferably the thickness of the top coat is in the range from approximately 25 to 125 microns (0.001-0.005 inches) with 25-50 microns (0.001-0.002 inches) being the generally desirable range, whereas the thickness of the thermal barrier coating may be in the range of approximately 75 to 500 microns (0.003-0.020 inches).
A thicker protective top coat does not necessarily extend the life of the thermal barrier coating. For example, an increased total ceramic thickness, that is the thickness of the ceramic protective top coat and the thickness of the thermal barrier coating may contribute to an increased sensitivity to thermal spalling, or a restriction in the proper flow of the combustion gases. In general the thicker the top coat, the more susceptible it is to failure due to fracture at the ceramic-metal interface or delamination under thermal cycling.
In certain operating conditions, which may involve particular temperature combinations or temperature and corrosive combinations, a thicker protective top coat may be useful. These conditions are more likely to occur in some industrial manufacturing conditions rather than in gas turbine operating environments. It should be noted that, if a thicker protective layer according to the present invention is required, the top coat and the thermal barrier coating may be graded to minimize internal stresses.
The thermal barrier coating may comprise yttria-stabilized zirconia (YSZ), alumina-titania, calcia stabilized-zirconia, magnesia stabilized-zirconia, ceria-stabilized zirconia (CSZ), scandia stabilized-zirconia, calcium silicate, calcium silicate zirconate blends, calcium-stabilized zirconia (CaSZ), zirconia toughened alumina (ZTA), alumina-zirconia, zirconium silicate, zircon, alumina or blends thereof, wherein YSZ is a preferred ceramic coat. In addition to its superior thermal insulating ability, YSZ also exhibits excellent adhesion properties under thermal cycling conditions.